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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Materials Data on Ca(CuN)2 by Materials Project

Ca(CuN)2 crystallizes in the tetragonal P-4m2 space group. The structure is two-dimensional and consists of one Ca(CuN)2 sheet oriented in the (0, 0, 1) direction. Ca2+ is bonded to four equivalent N3- atoms to form corner-sharing CaN4 tetrahedra. All Ca–N bond lengths are 2.41 Å. Cu2+ is bonded in a linear geometry to two equivalent N3- atoms. Both Cu–N bond lengths are 1.81 Å. N3- is bonded in a rectangular see-saw-like geometry to two equivalent Ca2+ and two equivalent Cu2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CuN by Materials Project

CuN crystallizes in the monoclinic Pm space group. The structure is one-dimensional and consists of two CuN ribbons oriented in the (1, 0, 1) direction. Cu3+ is bonded in a linear geometry to two equivalent N3- atoms. There is one shorter (1.72 Å) and one longer (1.73 Å) Cu–N bond length. N3- is bonded in a linear geometry to two equivalent Cu3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zn(CuN)2 by Materials Project

Zn(CuN)2 crystallizes in the tetragonal P-4m2 space group. The structure is two-dimensional and consists of one Zn(CuN)2 sheet oriented in the (0, 0, 1) direction. Cu2+ is bonded in a bent 150 degrees geometry to two equivalent N3- atoms. Both Cu–N bond lengths are 1.81 Å. Zn2+ is bonded to four equivalent N3- atoms to form corner-sharing ZnN4 tetrahedra. All Zn–N bond lengths are 2.10 Å. N3- is bonded in a see-saw-like geometry to two equivalent Cu2+ and two equivalent Zn2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Atomically Dispersed CuN x Sites from Thermal Activation of Boron Imidazolate Cages for Electrocatalytic Methane Generation

Atomically dispersed metal sites (ADMSs) have been recognized as promising candidates for electrochemical conversion. Among a diverse range of molecular precursors for ADMS synthesis, framework materials are particularly interesting due to their high degree of tunability and control over the primary coordination sphere of the metal ions. In this work, we demonstrate that a copper boron imidazolate cage, BIF-29(Cu), is a convenient precursor for a competent catalyst with isolated Cu sites coordinated by N donors for carbon dioxide electroreduction (CO 2 RR). Although BIF-29(Cu) exhibited moderate methane selectivity over hydrogen evolution reaction (HER), the methane selectivity is significantly enhanced by 2 times (55% CH 4 at –1.25 V vs RHE) after mild thermal activation. Extensive characterization methods indicate the transformation of crystalline BIF-29(Cu) into an amorphous carbonaceous material comprising isolated CuN x sites. Moreover, in situ X-ray absorbance spectroscopy indicates stable CuN x sites that are reduced during CO 2 RR. This work encourages the discovery of single-site electrocatalytic systems through a rational selection of molecular precursor and calcination parameters for promoting product selectivity.

10 SYNTHETIC FUELS↗
DOE OSTI2020

Materials Data on CuN by Materials Project

CuN is Zincblende, Sphalerite structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. Cu3+ is bonded to four equivalent N3- atoms to form corner-sharing CuN4 tetrahedra. All Cu–N bond lengths are 1.92 Å. N3- is bonded to four equivalent Cu3+ atoms to form corner-sharing NCu4 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CuN by Materials Project

CuN is Halite, Rock Salt structured and crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Cu3+ is bonded to six equivalent N3- atoms to form a mixture of edge and corner-sharing CuN6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Cu–N bond lengths are 2.08 Å. N3- is bonded to six equivalent Cu3+ atoms to form a mixture of edge and corner-sharing NCu6 octahedra. The corner-sharing octahedral tilt angles are 0°.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on CuN by Materials Project

CuN is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Cu3+ is bonded in a body-centered cubic geometry to eight equivalent N3- atoms. All Cu–N bond lengths are 2.26 Å. N3- is bonded in a body-centered cubic geometry to eight equivalent Cu3+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Al(CuN)3 by Materials Project

Al(CuN)3 crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Cu2+ is bonded in a square co-planar geometry to four equivalent N3- atoms. All Cu–N bond lengths are 2.04 Å. Al3+ is bonded to six equivalent N3- atoms to form corner-sharing AlN6 octahedra. The corner-sharing octahedral tilt angles are 0°. All Al–N bond lengths are 2.04 Å. N3- is bonded to four equivalent Cu2+ and two equivalent Al3+ atoms to form a mixture of edge and corner-sharing NAl2Cu4 octahedra. The corner-sharing octahedral tilt angles are 0°.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A Spectrochemical Series for Electron Spin Relaxation

Controlling the rate of electron spin relaxation in paramagnetic molecules is essential for contemporary applications in molecular magnetism and quantum information science. However, the physical mechanisms of spin relaxation remain incompletely understood, and new spectroscopic observables play an important role in evaluating spin dynamics mechanisms and structure–property relationships. Here, we use cryogenic magnetic circular dichroism (MCD) spectroscopy and pulse electron paramagnetic resonance (EPR) in tandem to examine the impact of ligand field (d–d) excited states on spin relaxation rates. We employ a broad scope of square-planar Cu(II) compounds with varying ligand field strength, including CuS 4 , CuN 4 , CuN 2 O 2 , and CuO 4 first coordination spheres. An unexpectedly strong correlation exists between spin relaxation rates and the average d–d excitation energy (R 2 = 0.97). The relaxation rate trends as the inverse 11th power of the excited-state energies, whereas simplified theoretical models predict only an inverse second power dependence. These experimental results directly implicate ligand field excited states as playing a critical role in the ground-state spin relaxation mechanism. Furthermore, ligand field strength is revealed to be a particularly powerful design principle for spin dynamics, enabling formation of a spectrochemical series for spin relaxation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Sub-Nanometer Nanoclusters of Copper Atop Single-Atom Copper Moieties toward Electrochemical CO 2 Hydrogenation to Methane

The electrochemical CO 2 reduction (eCO 2 R) offers a compelling route for converting CO 2 into value-added fuels and chemicals. Among CO 2 -derived products, methane (CH 4 ) occupies a distinct position, serving both as a key intermediate for emerging cascade electro-oxidation to oxygenates and as a strategically important extraterrestrial fuel that can be generated in situ from off-planet CO 2 resources. Although Cu-based catalysts capable of selectively producing CH 4 have been reported, they seldom sustain high selectivity at practically relevant current densities. Here, we created a single-step co-pyrolysis strategy toward generating and anchoring Cu sub-nanometer clusters (Cu SNC ) atop Cu-N x single-atom (SA) motifs embedded within N-doped carbon (NC), with controllable nanostructures through tuning of the synthesis parameters. Complementary spectroscopic analyses and density functional theory (DFT) calculations help reveal a structure−activity correlation that could guide the catalyst design. The Cu SNC @NC sample synthesized at 550 °C pyrolysis temperature (best described and modeled as Cu 3 -CuN 4 domains) represents the most effective combination of cluster size, metal-nitrogen coordination, and adsorption energetics needed to selectively promote CH 4 generation versus other eCO 2 R products. Incorporating pulsed electrolysis and hydrophobicity-modulated transport tuning at the triple-phase boundary (TPB) further enhanced CH 4 production achieving a partial CH 4 current density of ∼321 mA cm −2 , 53% Faradaic efficiency (FECH 4 ), and less than 4% combined FE for other eCO 2 R products, simplifying downstream CH 4 purification or upgrading. This work establishes generalizable principles for controlling Cu cluster atomicity and metal−nitrogen coordination, both of which are recognized determinants of CH 4 -efficient eCO 2 R.

CH4 production↗
DOE OSTI2025

In Situ Study of Resistive Switching in a Nitride‐Based Memristive Device

Abstract Resistive switching (RS) devices with ultra‐low‐voltage threshold and reliable switching repeatability exhibits great potential applications in energy‐efficient data storage and neuromorphic computing. Understanding switching mechanisms at nanoscale is critical to design RS devices with improved performance. In this work, a lamella memristive device using focused ion beam (FIB) method based on the metal/TiO x /TiN/Si structure device is fabricated. In situ transmission electron microscopy (TEM) and current–voltage ( I–V ) characteristic demonstrate that the lamella device shows a volatile RS behavior with a threshold switching at ≈ ± 0.4 V. In situ scanning transmission electron microscopy (STEM) experiments with electron energy loss spectroscopy (EELS) reveal that the charge carriers such as oxygen vacancies migrate under positive/negative DC bias and modulate Schottky barriers at the top and bottom metal/semiconductor interfaces. The RS mechanism of the lamella device is based on the Schottky barriers modulation and Joule heating assisted electric field triggered thermal runaway (FTTR) occurred at the metal/semiconductor interfaces. The fundamental insights gained from this study presents a perspective on interface‐type RS devices processing and opens up new technological opportunities of fabricating ultra‐low‐energy memristive devices.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Quantum Fluctuations and Lineshape Anomaly in a High‐ β Silver‐Coated InP‐Based Metallic Nanolaser

Abstract Metallic nanocavity lasers provide important technological advancement toward even smaller integrable light sources. They give access to widely unexplored lasing physics in which the distinction between different operational regimes, like those of thermal or coherent light emission, becomes increasingly challenging upon approaching a device with a near‐perfect spontaneous‐emission coupling factor . In fact, quantum‐optical studies have to be employed to reveal a transition to coherent emission in the intensity fluctuation behavior of nanolasers when the input–output characteristic appears thresholdless for nanolasers. Here, a new indicator for lasing operation in high‐ lasers is identified by showing that stimulated emission can give rise to a lineshape anomaly manifested as a transition from a Lorentzian to a Gaussian component in the emission linewidth that dominates the spectrum above the lasing threshold.

Koulas‐Simos, Aris↗
DOE OSTI2024

Highly efficient La/Ni co-doped strontium titanate catalyst for co-production of propylene and hydrogen from propane in protonic ceramic electrochemical cells

A highly efficient La/Ni co-doped strontium titanate (LSNT) perovskite catalyst is developed and integrated in a protonic ceramic electrochemical cell for co-production of propylene and high-purity hydrogen from commercial propane feedstock. Propane conversion and hydrogen production rate can be effectively enhanced under an applied current due to the electrochemical promotion effect and/or shifted reaction equilibrium induced by rapid separation of hydrogen product. Water vapor in the feed gas could significantly improve the catalyst stability by suppressing the coke formation. The propane conversion could reach up to 53% at 600 °C under a current density of 90 mA cm −2 . The LSNT catalyst also shows excellent tolerance for the sulfur contaminant in commercial propane gas. Finally, the excellent performance of the LSNT catalyst is attributed to the highly active and selective Ni species at the interface with the perovskite substrate, which are formed in situ via reduction-induced exsolution under reaction conditions.

interfacial active sites↗
DOE OSTI2025

Effects of iron carbide crystal phases and dopants on the conversions of CO 2 into ethylene

The density functional theory method was used to investigate the conversions of CO 2 to ethylene formation on two common iron carbide surfaces: Fe 3 C(0 1 0) and Fe 5 C 2 (1 1 1). Based on the structure relaxation of reaction intermediates and the elementary reaction transition states. We deduced the most competitive reaction pathways for ethylene production. The main CO 2 -to-ethylene routes and the competition of side products, CO and CH 4 , are discussed. Our analyses showed that CO 2 conversion is surface structure sensitive, whereas CH 4 and C2+ hydrocarbon formations depend on the reactivity of native C atoms in the carbides. To modify the intrinsic catalyst performance, mixing dopants in Fe catalysts is an effective strategy. Furthermore, we demonstrate that doping Zn and Zr can alter the local electronic structure and enhance CO 2 adsorption on the catalyst surface.

CO2 hydrogenation↗
DOE OSTI2022

Nanostructured carbon as highly efficient and stable anodes for ethylene production and power generation in protonic ceramic electrochemical cells

Protonic ceramic electrochemical cells (PCECs) have the potential in reducing the energy input and carbon emissions in ethylene production from ethane dehydrogenation. The performance of conventional perovskite-based anode materials for ethane conversion in PCECs is limited by their low active surface area and proneness to coke deposition. In this work, for the first time, we demonstrate the use of aligned carbon nanotube forests (CNTFs) as a novel anode material for an ethane fueled PCEC to co-produce ethylene and electricity. The CNTF electrode was grown on the electrolyte by the chemical vapor deposition (CVD) method. Highly dispersed iron carbide nanoparticles are formed in situ on the CNTFs during the CVD process, acting as highly active catalysts for ethane dehydrogenation. The novel PCECs show superior catalytic and electrochemical performances to that using conventional perovskite-based anodes. The cell also exhibits excellent durability and anti-coking abilities within 100 h test. This work showcases the promising application of nanostructured carbon, a new class of non-perovskite materials, as the multifunctional electrode materials for PCECs.

03 NATURAL GAS↗
DOE OSTI2021

Mechanistic understanding of support effect on the activity and selectivity of indium oxide catalysts for CO 2 hydrogenation

Herein we present a mechanistic study on the support effect (ZrO 2 and CeO 2 ) of In 2 O 3 catalysts in CO 2 hydrogenation by a combined experimental and computational approach. Kinetic experiments and surface characterization suggested that the activity of In 2 O 3 catalysts cannot be simply correlated with the abundance of surface oxygen vacancies (O v ) formed by either H 2 -reduction or thermal treatment, which has been frequently invoked in previous studies. The support effect should originate from the electronic interactions between In 2 O 3 and the support oxide, rather than geometric factors or the difference in the particle size of In 2 O 3 . Theoretical modelling revealed that surface O v facilitate the formation and stabilization of the formate (HCOO*) intermediate. While a carbonate-like structure is favored for CO 2 adsorption on CeO 2 -supported or unsupported In 2 O 3 catalysts, CO 2 tends to bind strongly in a bent configuration on the O v site at the In 2 O 3 -ZrO 2 interface. The distinct CO 2 adsorption structures on different supported In 2 O 3 catalysts may account for the different reaction energy profiles in the subsequent hydrogenation reactions, especially the rate-limiting step, i.e., hydrogenation of HCOO* to CH 2 O* and methoxy (CH 3 O*). The relatively higher methanol selectivity of In 2 O 3 catalyst supported on ZrO 2 with respect to that on CeO 2 are suggested to stem from the greater energy difference (Δ$E_a$) between the parallel hydrogenation and C-O bond cleavage of HCOO*, which leads to the formation of methanol and CO, respectively. We report this study underlines the important role of metal-oxide-interface in determining the catalytic behavior of oxide-supported In 2 O 3 catalysts in CO 2 conversion.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Boosting the performances of protonic solid oxide fuel cells for co-production of propylene and electricity from propane by integrating thermo- and electro- catalysis

Protonic solid oxide fuel cells (p-SOFC) integrated with clean thermal energy sources are promising platforms for decarbonized chemical production in addition to power generation, such as on-purpose propylene production from propane dehydrogenation (PDH). The catalytic performance of the conventional nickel-cermet-based anode materials in p-SOFC for propane conversion is restrained by their low active surface area and proneness to coking. In this work, by integration of a highly efficient industry-relevant thermal catalyst PtGa/ZSM-5 for PDH reaction, we demonstrate that both the electrochemical and catalytic performance of the propane-fueled p-SOFC can be effectively enhanced. The PtGa catalyst integrated p-SOFC exhibits a peak power density of 93 mW cm -2 at 600°C, which is greater by about 100% and 50% than that without catalyst or with a perovskite-based (Pr 0.3 Sr 0.7 ) 0.9 Ni 0.1 Ti 0.9 O 3 (PSNT) catalyst layer, respectively. The PDH activity and olefin selectivity of the PtGa catalyst is also significantly higher than that of the PSNT catalyst. In addition, much improved coke tolerance and propylene selectivity (over 90%) compared to the catalyst-free Ni-cermet anode materials were achieved by integrating the industrial catalyst layer. The propane conversion can be further improved by an applied current density, whereas the olefin selectivity is almost unaltered. The excellent performance of the PtGa catalyst integrated p-SOFC is attributed to the high surface area, intrinsically high catalytic activity, selectivity, and anti-coking properties of the catalytic layer for propane conversion. In conclusion, this work provides a general approach and a case study for boosting the performances of p-SOFCs in chemical production by integrating thermo- and electro- catalysis.

30 DIRECT ENERGY CONVERSION↗